TWI305537B - Organic compounds having a core-shell structure - Google Patents

Description

1305537 A7 B7 V. INSTRUCTIONS (i) 10 15 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printing 20 The present invention relates to an organic material containing a core-shell structure, to a method for its preparation, and to its use as a semiconductor in electronic components. . In the past 15 years, with the discovery of organic conductive compounds and semi-conductive organic compounds, the field of molecular electronics has developed rapidly. During this period, many compounds with semiconducting properties and electro-optical properties were discovered. It is generally believed that molecular electronics will not replace traditional germanium semiconductor components. On the contrary, it is believed that molecular electronic components can open up new applications that require large-area coatings, structural flexibility, and low-temperature, low-cost processing. At present, semi-conductive organic compounds have been applied in the field of organic field effect transistors (OFETs), organic light-emitting diodes (〇LEDs), sensors, and optoelectronic components. The combination of the sinking material onto the organic semi-conducting volume circuit has made it impossible to find a low-cost solution to the problem of the smart card or price sign problem that has been technically difficult due to the lack of flexibility in price and frequency components. At the same time, germanium FETs can be used as circuit components for large area flexible substrate displays. Regarding organic semiconductors, semiconductor integrated circuits and their applications are reviewed in Electronics, pp. 2, 2, 15 and 38. A field effect transistor is a component having three electrodes, and the conductivity of the small conductive path between the two electrodes (that is, the "source" and "drain") is separated by a thin insulating layer. The electrodes (also known as the "gates") are controlled. The most important characteristic of the FET is the movement characteristic of the charge carrier, which plays an important role in the switching speed of the transistor, the ratio of the current in the on and off states, i.e., the "on/off ratio". There are two major types of organic matter in the organic % effector. These organics contain long common units, which are divided according to molecular weight and structure. The paper is calibrated to the Chinese National Standard (CNS) A4 specification (210x297 public fantasy 1305537).

Conjugated polymers and conjugated oligomers. Oligomers usually have a uniform molecular structure and a knife amount of less than 1G 'GGG Dalton. The chelate usually contains a bond of a homo-repeat unit and a molecular weight distribution but 'has between the oligomer and the polymer. Continuous transition. 5 The distinction between oligomers and polymers is often reflected in the fundamental difference in the processing of these compounds. The oligomers are typically vaporized and applied to the substrate by agro-phase deposition. The term polymer generally refers to compounds that do not evaporate, so regardless of their molecular structure, they are applied by other methods. For polymers, it is usually necessary to dissolve in a liquid medium, such as in an organic solvent, and then apply it in a corresponding manner. For example, a commonly used application method is spin coating. A particularly preferred method of applying a semiconductive compound is by an ink jet method. In this method, the conductive solution is dropped onto the substrate in the form of very fine droplets and then dried. This method allows the formation of a structure during application. This method of applying a semiconducting compound has been described, for example, Nature 401, page 685. Knowing that 5, / Yan chemical law is considered to have greater potential in obtaining cheap organic semiconductor integrated circuits through simple methods. An important prerequisite for the production of quality organic semiconductor circuits by the Ministry of Economic Affairs, the Intellectual Property Office, and the Consumers’ Cooperatives. A compound with a particularly high purity. Ordering phenomena in semiconductors play an important role. The uniform arrangement of the compound 20 and the apparent grain boundaries result in a significant decrease in semiconductor characteristics. Therefore, organic semiconductor circuits produced without the use of particularly high purity compounds are generally unusable. For example, residual impurities can inject charge into the semiconducting compound ("doped"), thereby reducing the on/off ratio, or significantly reducing its conductivity as a charge scavenger. The scale applies to China·§·^·(ΟΝ3)Α4 specifications (21〇χ297 public love^-------- 1305537 A7 B7 5. Invention description (3) Reaction of semi-conductive compound and oxygen, oxidation 'can oxidize semi-conductive compounds, thus shortening the possible storage, processing and working life. The generally required purity is usually not achieved by known polymer chemistry methods such as washing 're-precipitation and extraction. 'Molecularly uniform and generally volatilizable oligomers can be relatively easily purified by sublimation and chromatography. Important representatives of some semiconductive polymers are described below. Polyfluorenes and copolymers, for example, poly(9) ,9-dioctylfluorene-co-biporphyrin)(1) 10

(I) The printing of the consumer cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs has reached the charge mobility of 〇_〇W/Vs ("Community & Regional Rules, Volume 290, page 2123"), hereinafter referred to as mobility, M. (3-hexylthiophene-2,5-diyl)(11)

This paper scale applies to the Chinese Standard (CNS) A4 specification (210x297 mm) A7 B7 1305537 V. Invention description (4) Already can achieve a mobility of 0.1cm2/Vs (Science, 1998, 280, 1741) page). The copolymer of polyfluorene and fluorene and poly(3-hexylthiophene-2,5-diyl), like virtually all long-chain polymers, form a high-quality film after application from a solution, and thus are easy to process. However, high molecular weight polymers having a molecular weight distribution cannot be sublimed by vacuum and can only be purified by chromatography, and there are still some difficulties. An important representative of oligomeric semiconducting compounds, such as oligothiophenes, especially those having a terminal alkyl substituent, represented by formula (III), 10

Order

(IV) Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, and 2,3,6,7-dibenzopyrene (IV) 0!,0!'-dihexyltetradecene The typical mobility is 15 0.05-0.1 cm 2 /Vs. The mesophase, especially the liquid crystal phase, plays an important role in semiconducting organic compounds, but scientists have not yet fully understood this field. For example, the mobility of α,α'-dihexyltetrathiophene crystals is the highest reported so far (Chem. Mater., 1998. Vol. 10, page 457), and these crystals are from a double denature 20 at 80 ° C. Crystallization in the liquid crystal phase (Synth. Met., 1999, 1〇1 -6- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210x297 mm) 13〇5537

DESCRIPTION OF THE INVENTION (6) 5 10 15 The compound is particularly suitable for large-area coating. Compounds that form high quality uniform thicknesses and morphologies are necessary to suit electronic applications. It has now surprisingly been found that an organic compound having the desired properties has a core composed of a multifunctional unit and a core of a linear conjugated oligomeric chain having a flexible non-conjugated chain at its end. _ shell structure. Accordingly, the present invention has prepared a core-shell structure compound which is characterized by a core composed of a multifunctional unit and a linear conjugated oligomeric chain having a flexible non-conjugated chain at its end. In a preferred embodiment, the compounds of the invention are oligomers or poly-humans. . According to the invention, this core-shell structure is at the molecular level, that is, it relates to the structure of a molecule. For the purposes of the present invention, the end point link of the linear conjugated oligomeric chain is the point of the linear conjugated oligomeric chain in the end point unit of which no such other chain exists. Employee Consumption Cooperative Printed 20 The compound of the present invention preferably has a core-shell structure K-(-L-R)n (Z) represented by the chemical formula (Ζ) wherein κ is an η-functional core L is a linear conjugated oligomeric Chain R is linear or branched C2-C2 (r-based monounsaturated or polyunsaturated paper scale applicable to China National Standard (CNS) A4 specification (210x297 mm) [305537 A7 B7 V. Description of invention (0 c2 -c2❶-thin base 'CVCV county base, low polyether base' or C2~C2〇-polyether base η is an integer greater than or equal to 3, preferably an integer greater than or equal to 6. The shell is supported by η by R Linear conjugate chain B. For example, if n is 3 or 6, this is the structure represented by the chemical formula (2 3) or (z 6)

R I L R— LIU KILIR L/〆”

4 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing (Z-3) (Z-6) where K, L and R are defined as above. In the structure of this compound, a core composed of polyfunctional units, for example, has a branch The core of the chain, the linear conjugated oligomeric chain and the ductile non-conjugated chain are connected to a core composed of polyfunctional units having a dendritic structure or a super-multi-branched structure. Super multi-branched structures and their preparation are well known to those skilled in the art. Super multi-branched polymers or oligomers have a unique structure that is determined by the monomer structure used. The monomer used is an ABn monomer, i.e., the monomer has two different functional groups A and B. Among them, the functional group A exists only one in one molecule, and the other energy group B appears multiple times (n times). These two functional groups A and -9- are suitable for use in the National Standard (CNS) A4 specification (210 X 297 mm) ---

A7 B7 1305537 V. Inventive Note (8), B can react with each other to form a chemical bond, that is, it is polymerized. The structure of the monomer 'polymerizes to form a branched polymer having a dendritic structure, i.e., a super multi-branched polymer. Super-branched polymers have no regular branching points, no rings, and no B-functional groups at the ends of the chains. Super multi-branched polymers, their structure, branching problems and nomenclature are already in L.J. Mathias, T.W.Carothers,

Adv. Dendritic Macr〇mol. (1995) 2 1〇1_121 is described in the example of a ruthenium resin based on ruthenium resin, and these studies are hereby cited. For the purpose of the present invention, the preferred super-multi-branched structure is super-branched. polymer. 1〇 However, the core composed of polyfunctional units is particularly preferably a tree-structured structure, which is particularly suitable due to their regular composition. The Ministry of Economic Affairs Intellectual Property Office employee consumption cooperative printed by the purpose of the present invention that the dendritic structure is a synthetic macromolecular structure formed by two or more monomers connecting previously connected monomers step by step, therefore, the group is single Each step of the number of bodies is exponentially growing, and the last 15 results in a globular branch structure. This forms a three-dimensional macromolecular inclusion of the branches and a regular stretching structure from the center to the periphery. This structure is usually formed layer by layer by a method well known to those skilled in the art. The number of layers is often referred to as the generation. The number of branches per layer and the number of end groups increase with generation. Dendritic structure preparation and nomenclature have been well known and described by those skilled in the art 20 and are described, for example, in Dendrimers and Dendrons, Wiley-VCH, Weiheim, 2001 by G. R. Newkome et al. Useful structures in the nucleus consist of dendritic structures, hereinafter also referred to simply as dendritic nuclei, in principle those described in U.S. Patent 6,025,462. For example, these are super-branched structures, such as polyphenylene, polyether oxime, -10-. The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) [305537 A7 B7 10 15 Ministry of Economics Printed by the Bureau of Employees' Consumer Cooperatives, Inc. 20, Inventions (9) Polyesters, as described in USA 5, 183, 862, USA 5, 225, 522 and USA 5, 270, 402, as described in USA 5,264,543, Polyamines as described in U.S. Patent No. 5,346,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Shaped structures such as the polyaryl aryl groups, poly-arylene ethers, or polyamine amines described in U.S. Patent No. 4,435,548, issued to U.S. Patent No. 4,507,466, the disclosure of which is incorporated herein by reference. . However, other structural units can also be hung to form a dendritic core. The dendritic nucleus acts primarily to form a number of different functional groups to form a matrix to which a linear conjugated oligomeric chain is attached to form a core-shell structure. Linear conjugated oligomeric chains are predetermined by attachment to the substrate, and their effects are therefore increased. Dendritic nuclei have a range of functionalities - that is, junctions - that are suitable for connection to conjugated oligomeric chains. According to the invention, the dendritic core and the core composed of the super-multi-branched structure have at least three, and preferably at least six different, official b-degrees. The preferred structure of the dendritic core is a 1,3,5-phenylene unit (chemical formula v_a) and a chemical formula (Vb) to the chemical formula (Ve), and a plurality of identical or different units of the chemical formula (Va) to (Ve) are mutually connection. 11- A7 B7 1305537 V. Description of invention (10

(V-a) «

CH Si (V-c)

Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperative Printed (V*e) The chemical formula (V-a) to (V-e) and the chemical formula used below are marked by the * mark as the connection point. The units of (V-a) to (V-e)f are connected to each other or to the linear co-light oligomeric chain. An example of a dendritic core composed of units of the chemical formula (V-a) is as follows:

The point of attachment to the linear conjugated oligomeric chain occurs at the position marked with an *. The shell of the compound of the present invention is formed by a linear conjugated oligomeric chain attached to the core. Suitable linear conjugated oligomeric chains in principle have all chain structures of oligomers or polymers known to be electrically conductive or semiconductive. They are, Example-12- This paper scale applies to China National Standard (CNS) A4 specification (210x297 mm) 1305537 A7 B7 V. Description of invention (11), substituted or unsubstituted polyaniline, polythiophene, poly-extension The bis(oxydithiophene) is agglomerated, poly-big, poly-b-block, poly-iso-naphthyl, and polystyrene. These are used as homopolymers or homooligomers or as copolymerization. Or co-oligomers. These preferred examples of linear conjugated oligomeric chain structures are those consisting of units represented by 2 to 1 Å, especially 2 to 7 chemical formulas (VI_a) to (VI_e),

(Vl-a)

(V|.C) (Vl-b)

The R1 'R2 and R3 printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs may be the same or different, each of which is a hydrogen atom or a linear or branched cvc^alkyl group or a branched chain (the alkoxy group, the most Preferably, they are all identical and all are hydrogen atoms. The soils R4 may be the same or different, each being an argon atom or a linear or branched Ci-Czo-alkyl or branched CrCw alkoxy group, preferably hydrogen 15 Atom or a C6-C12-alkyl group, R5 is a hydrogen atom or a methyl or ethyl group, preferably a hydrogen atom. 10 -13- This paper scale applies to the Chinese National Standard (CNS) A4^1~^1〇 Χ297,^53

1305537 V. INSTRUCTIONS (12) \ Chemical formula οα-a) to (VI_e) The unit in the division KV-e) marked by * is passed through them :::. ^Polymer' or at the end of the chain through the axis of the nucleus = a tough non-co-light chain. It is good to have a substituted or unsubstituted 2,54% HVT-(VI-b) unit, or a substituted or unsubstituted ’. -a) or 3 um, digit 2'5_ or two orders 1::: 1 〇 = = B 2,5__ ♦ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

P is from 2 to 10, preferably from 2 to the integer of ^7 represented by R in the chemical formula (Z). The chain point is protected by a flexible non-conjugated chain. The conjugated oligomeric chain is Those endpoints have high (internal) molecular mobility and social, ^. A flexible chain refers to the solubility "increased by the reaction of the solvent molecule for the purposes of the present invention. 'Flexibility refers to (internal) points (Z-6-1) 15 This paper size applies to National Standards (CNS) A4 specifications -14- 305537

, invention description (sexual total oligomeric chain formed at the end of the chain of the soft and de-silk. ', cup, f can be embedded with oxygen atoms of aliphatic saturated or unsaturated 5 groups < a family or an oxy-aliphatic group, that is, an alkoxy group with a branched chain of oxygen atoms intercalated, such as an oligoether or a group, a n-hexyloxy group, a n-heptyloxy group, a n-octyloxy group 10 and a positive twelve-filament 1 From the preferred embodiment of the invention, it is preferred that the preferred embodiment of the invention has a ruthenium 3 ς base unit in the dendrite, 2 to 4 thiophenes or 3,4 _ ethyl oxirane = low (tetra) phenanthrene or oligomeric ( 3,4_extended ethyl dioxin) unsaturated ^ is a linear conjugated oligomeric chain, and even-alkyl is a flexible non-conjugated = 15 compound. The chemical formulas of Saki (XII) and (XIII) The two compounds are described below.

(XI Ρι〇Η21

Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives. This paper scale applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Ϊ305537

Description of the invention (Η)

The Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, printed the compound of the present invention is electrically conductive or semi-conductive. According to the present invention, 'a semiconductive compound is preferred'. A compound having a mobility of at least 10-4 cm 2 /Vs is optimal. The organic compound of the present invention can be easily dissolved in a general solvent such as gas, toluene, diethyl ether, dioxane or tetrahydrofuran, and thus is very suitable for processing in a solution. It is particularly surprising that the compounds of the invention have a very simple simplicity of unsaturated thiophenes or 3-oxime ethyldioxane units in the linear conjugated oligomeric chain, and (iv) order and shape-off-16-1305537 A7 B7 V. Description of invention (15) --- Not = side, broken. Therefore, the organic compound of the present invention has good electrical properties of 14 ▲ and very good film formation. Therefore they are very suitable for large area coating. Further, the organic compound of the present invention has non-ten good thermal stability and good anti-aging properties. In principle, the compounds of this month can be prepared by two different routes, namely the preparation methods of convergence and divergence. In the preparation method of convergence, the linear co-oligo-oligomer chain is retained by the non-co-armile flexible chain prepared in the first step. In the case of a dendritic nucleus, it is attached to a structural unit called a single branch: that is, a structural unit containing a portion of the dendritic structure and a new connection (4) into a dendritic structure. Many of the single branches are joined in the final step of the preparation to form the final structure. In the divergent preparation method, a dendritic core or a core comprising a super-multi-branched structure is prepared in the first step. A linear co-decent oligomeric chain maintained by a non-common bouncy chain can be attached to the core in the next step. 15 As regards the properties of the compounds of the invention, the preparation process is in principle unproductive. Many variations may occur in the preparation methods already described. Thus, for example, it is possible to change the sequence of individual preparation steps and, for example, the Ministry of Economic Affairs, the Intellectual Property Office, the Consumer Cooperative, to print the non-conjugated flexible chain and the linear conjugated oligomeric chain as the final step in the preparation. 20 However, depending on the structure to be produced, for example, it is effective to join the non-co-rubbery flexible chain and the linear co-armile oligomeric chain in the preparation, since the flexible chain increases the solubility of the structural unit, so It facilitates the preparation of the compounds of the invention. In principle, those who are proficient in this method are familiar with a series of chemical reactions to -17- 1305537 A7 B7. V. Inventions (16) 5 10 15 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Print 20 for formation of multi-functional units The nucleus, which is linked to a linear conjugated oligomeric chain, and a series of chemical reactions that attach a non-conjugated flexible chain to these. The invention therefore also provides a process for the preparation of the compounds of the invention, which is characterized by the preparation of an organometallic reaction. For organometallic reactions, it is necessary to introduce suitable functional groups onto dendritic or super-branched nuclei, to which linear conjugated oligomeric chains and flexible non-conjugated chains are attached. For example, these groups are halogens such as gas, bromine, male, preferably desert, organotin groups such as trimethyltin or triethyltin groups, and organic stone groups such as trimethyl sulphide Or a tetramethyl group, or an organic boron group such as boric acid. Particularly preferred organometallic reactions for coupling the individual components of the compounds of the invention are the use of two desert groups by a Grignard reagent, for example, a U-bis(diphenylphosphino)ferrocene digas peak. Kumada coupling, and: the shed group under the basic conditions and the coupling. Those who are proficient in this method are well-known to carry out these steps, and the intermediates in the step-by-step process are prepared. The intermediates are prepared in the step (4). The most compounds are: =, the two methods are known: steaming, rising τ Heavy... daily stroke, re-precipitation, washing or sonar. The system is based on it 18- winter paper ruler with T Guan Jia Pi (CNS_-(2Ϊ0χ297"^Τ 1305537 A7 _______ B7 5, invention description (17), making us suitable for application in semiconductor technology. The compound of the invention It is possible to form a mesophase (mesomorphous state), that is, a physical state between a solid state and a liquid state. This also relates to a liquid crystal phase and a compound which contributes to predetermining the present invention. The compound of the present invention is preferably at 5 〇. C 5 to 30 〇 C, particularly preferably 80 ° C to 180 ° C to form a liquid crystal phase. The compound of the invention can be dissolved in at least 0.1%, preferably at least 1% 'particularly preferably at least 5% Commonly used solvents, for example, gas, toluene, benzene, diethyl ether, dioxane or tetrahydrofuran. The compounds of the present invention are capable of forming a high quality film of 10 layers of uniform thickness and morphology 'so suitable for electronic applications. Finally' the invention also provides The compound of the present invention is a compound of a semiconductor in an electronic component such as a field effect transistor, a light-emitting element such as an organic light-emitting diode or a photocell 'laser and a sensor. For these purposes, the compound of the present invention is the most It should be used in the form of a film. Printed by the Ministry of Economic Affairs, Intellectual Property Office, Employees' Cooperatives, in order to make them function effectively as semiconductors, the compounds of the present invention have sufficient mobility, such as at least lOWWs. For applications, the compounds of the present invention are applied. On a suitable substrate, for example, a wafer, a polymer film, or a glass sheet provided in electricity or electrons. In principle, it can be applied by all 20 application methods. The compound of the present invention is preferably in the liquid phase. Also, in particular, it is applied in a solution, after which the solvent is vaporized, and the solution is applied by a known method, for example, spraying, dip coating, printing, and blade coating, preferably by through coating and ink jet method. ° The layer of the compound of the present invention can be further worked after application, and the paper size is applicable to the national standard (CNS) A4 specification (210 X 297 public) 1305537 A7 B7 5. Invention description (18), such as By heat treatment 'for conversion, for example by liquid crystal phase, or for construction, for example by laser ablation. Further, the invention provides a compound of the invention comprising as a semiconductor Sub-element. 5 Example 5 - Mercapto-2, 2': 5', 2" Triple porphine (Synthesis, 1993, page 1099; Chem. Mater., 1993, Vol. 5, 430) (3,5-II Bromophenyl)trimethyldecane (J. Organomet. Chem., 1983, Vol. 215, p. 149) has been prepared using the known procedure of the present invention. Example 1: (contains a linear co-armed oligomeric chain and Intermediate of the end chain) t Βγ-Μ9^^Τ^Ο10Η21 (VH) 15 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing (5··-癸基-2,2':5',2"triple thiophene- Preparation of 5-yl)magnesium bromide (乂11): butyl chain (1.6M n-BuLi dissolved in 8.8πύ, 14.0mmol hexane) was added to the 5-mercapto-2,2':5' by syringe , 2" Trithiophene (6.6 (^, 14.4111111 〇 1) in anhydrous THF (100 mL), at 2 under N2. (: Stirring. After the completion of the dropwise addition, the solution was heated to room temperature (23 ° C) and stirred for another hour. Then cooled to 2 C ', immediately added MgBr2-Et2 〇 (3.67, 14.2 mmol). The reaction mixture was heated again. Stir at room temperature for an additional hour. (5"-mercapto-2,2,:5,,2"trithiophen-5-yl) magnesium bromide was not isolated, and the resulting solution was used directly in the -20 - This paper size applies to the National Standards (CNS) A4 specification (210x297 mm). 1305537 V. Description of the invention (19) A7 B7 One-step reaction example 2 (Preparation of single-branched intermediates of the chopping functional group)

Preparation of [3,5-bis 5''-fluorenyl-2,2,:5,,2"triple sin·5·yl)phenyl](trimethyl)-arcane (VHI). Fresh preparation 5_Mercapto-2,2,:5,,2"trithiophene (14.0 mmol) in anhydrous THF (Example 1} solution was added dropwise at room temperature (3,5-dibromobenzene) trimethyl Base decane Q 54g5mm 〇 1) and pd (dpp illusion Clz -Ci 〇 H21 (Vin) 10 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 15 pressure method (70mg '0.1mmol) (dppf = diphenyl phosphine) dissolved in 5 〇ml in anhydrous THF. After the addition was completed, the solution was stirred for another two hours. The completion of the reaction was monitored by TLC. The reaction mixture was poured into 3 ml of cold anhydrous diethyl ether, then 2 〇〇ml was added. 20 ml of 1 M (1 mol) of chilled water of HCl. The ether phase containing the yellow precipitate (the desired product) was separated and washed three times with 100 ml of ice water. The ether phase was filtered through a G3 glass screening procedure. It was washed 3 times with 50 ml of cold anhydrous diethyl ether and dried. This gave 3 - 36 g of dark yellow crystalline crude product. Purified by column chromatography (eluent: n-hexane / chloroform 4:1) at 40 ° C In Zheng-21- This paper scale applies to the national standard (0^) 八4 specification (2丨Ox297 mm) A7 B7 1305537 V. Invention description (20) 'Recrystallization in hexane, finally 2.64g light Yield: 57%. Melting point: 120 ° C. bNMRGOO MHz, CDC13, TMS/ppm): 0.353 (s, 9H), 0.884 (t, 6H, J = 6.9), 1.20-1.45 (superimposed peaks, 28H), 1.688 (m, 4H, J = 7.3, M = 5), 2.798 (t, 4H, J = 7.6), 5 6.692 (d, 2H, J = 3.9), 6.696 (d, 2H, J = 3.9 ), 7.021(d,2H,J=3.9), 7.109(d,2H,3.9), 7.156(d,2H,3.4) > 7.287(d,2H,3.9), 7.623(d,2H,J= 2.0 ), 7.763 (t, lH, J = 1.7). Example 3: (Preparation of preparation of boron-functional mononuclear intermediate) 10

H, C CH, ^10^21 (IX) Book 4 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 2-[ 3,5-bis(5"-mercapto-2,2^ 5',2" triple thiophene Preparation of -5-yl)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborane (IX): 100 ml three-necked round bottom flask connected to a reflux condenser The plate and the protective gas inlet are filled with N2. 15 compound (VIII) (2.31 g, 2.5 mmol) and 40 ml of anhydrous tetra-methane were added. Next, 5 ml of a 1 MB Br3 tetraoxane solution was added through a septum with a disposable polypropylene syringe, and the reaction mixture was refluxed for 40 hours. Then mix the reaction -22- This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1305537 A7 B7 V. Invention description (2i), cool to room temperature and transfer to 500ml with syringe containing 250ml lM NaOH The solution is in an Erlenmeyer flask. After adding 2 ml of water, the mixture was stirred vigorously, the aqueous phase was decanted, and the residual wet salt was suspended in a mixture of diethyl ether (2 〇〇mi), THF (100 ml) and 2M HCl (300 ml). The mixture was stirred vigorously for 3 hours until two phases were formed. The ether phase was separated, the aqueous phase was washed with diethyl ether, and the mixed ether phases were washed three times with 100 ml of water, dried over Na 2 SO 4 , and the solvent was removed with a rotary evaporator. Thus, 4 g of a wet brown solid boronic acid derivative was added, and pinacol (330 mg, 2.75 mmol) and 1 ml of anhydrous benzene were added. The mixed 10 was refluxed overnight using a Dean-Stark apparatus (卞 separator). After cooling and removing the terpene on a rotary evaporator, 3 g of a crude product in the form of a brown solid was obtained. After purification by column chromatography (eluent: toluene), 2.64 g of dark yellow crystals were obtained. Yield: 61%.咕NMR (400 MHz > CDC13 » TMS/ppm): 0.884 (t, 6H, J = 6.9), 1.20 - 1.45 (overlapping peak, 28H), 1.388 (s, 12H), 1.688 (m, 4H, M = 5, J = 7.5), 15 2.798 (t, 4H, J = 7.6), 6.692 (d, 2H, J = 3.4), 6.995 (d, 2H, J = 3.4), 7.071 (d, 2H, J = 3.9 ), 7.104(d,2H,3.9), 7.148(d,2H,3.9) 7.334(d,2H,3.4), 7.868(t,lH,J= 1.7), 7.935(d,2H,J=2.0) Economy Ministry of Intellectual Property Bureau Staff Consumer Cooperative Printed Example 4: (Preparation of decane-functional mononuclear intermediate) -23- This paper scale applies to China National Standard (CNS) A4 specification (210X 297 public Chu) 1305537 A7 B7 V. Description of the invention (22)

Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed trimethyl [3,3",5,5"-four (5"-癸基_2,2,:5,,2"triplethiophen-5-yl) 1 Preparation of 1,1,3,indole-terphenyl-7-yl]decane (X): 1 〇〇ml three-necked flask connected to magnetic stirrer, reflux condenser, protective gas inlet and septum under n2 5 Add (3,5-di-diphenyl) tridecyl decane (2 called '0; 7 job 〇 1). Then add Pd(PPh3)4 (l7〇mg, in the glove box, the glass device is installed and Remove from the glove box and then prepare a solution of compound (IX) (147 g, 1.5 mmol) dissolved in 30 ml of toluene and Na2CO3 (2Maq. (aqueous phase), i〇ml), and then deoxidize by means of N2. The reaction mixture was refluxed for 36 hours under N2. Then, the reaction mixture was cooled to room temperature, poured into a flask containing 100 ml of water and 300 ml of CH2Cl2. The organic phase was separated and the aqueous phase was washed with 100 ml of CH.sub.2Cl. The phases were washed with water, dried over MgSO4 and evaporated. The product was purified by recrystallization from 4:1 n-hexane/methanol mixture to give 15 to 763 mg brown solid. Pure product in the form. Yield: 59%. Melt-24- This paper scale is applicable (210x297 ^11 A7 B7 1305537 V. Invention description (23), point: 158 ° C. GPC (polystyrene standard): MP=1540. 4 NMR (400 MHz, CDC13, TMS/ppm): 0.421 (s, 9H), 0.882 (t, 12H, J = 7.1), 1.20-1.45 (overlapped peak, 56H), 1.684 (m, 8H) , M = 5 J=7.6), 2.792(t,8H,J=7.6), 6.684(d,4H,J=3.9), 5 6.992(d,4H,J=3.4), 7.012(d,4H,3.9 ), 7.117(d,4H,3.9), 7.179(d,4H,3.4) 7.369(d,4H,3.4), 7.753(d,4H,J=1.5), 7.802(d,2H,J=1.5) &gt 7.816 (t, 2H, J = 1.5), 7.865 (t, lH, J = 1.7). Example 5 (Preparation of boron-functional mononuclear complexes) 10

Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 4,4,5,5-four 曱基-2-[ 3,3",5,5"-four (5·,-癸基-2,2, : 5 ,,2"Trithiophen-5-yl)-1,Γ:3,,Γ-terphenyl-5'-yl]-1,3,2-dioxaborane (XI) Preparation: Compound (X) (610 mg, 0.33 mmol), 2 ml of 1 M BBr3 dissolved 15 solution in tetrafluoroanthracene and pinacol (44 mg, 0.37 mmol) was carried out by -25-

This paper size applies to the @Standard (CNS) A4 specification (210x297 public D 1305537 A7 B7 5. Inventive Note (Prepared by the procedure described in 24 Example 3) The washing step described in Example 3 and drying under reduced pressure A crude product of 65 mg of a brown solid was obtained. After purification by column chromatography (eluent: benzene), 3i y y y y y y y y y y y y y y CDC13, TMS/ppm): 0.882 (t, 12H, J = 7.1), 1.20 - 1.45 (overlapping peak, 56H), 1.683 (m, 8H, M = 5, J = 7.6), 2.790 (t, 8H, J =7.6) , 6.682 (d, 4H, J = 3.4), 6.987 (d, 4H, J = 3.4), 7.001 (d, 4H, 3.9), 7.112 (d, 4H, 3.9), 7.175 (d, 4H, 3.9), 7.374 (d, 4H, 3.9), 7.785 (d, 4H, J = 2.0), 7.799 (t, 2H, J = 1.7), 7.988 (t, l, J = 1.7), 8.123 (d, 2H, J=1.5). 10

Example 6 (Example of Preparation of Compound According to the Invention)

Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, printing

-2 4 Scale applicable ^ National Standard (CNS) A4 specification (210 X297 mm) Ϊ305537 V. Invention description (25), 1,3,5-three [3,5-double (5,,·癸基_ 2., 2,: 5,, 2 "Trithiophene-5-yl)phenyl]benzene (XII) Preparation: Compound (IX) (450 mg, 4.6 x l 〇 -4 mol), 1, 3, 5 - 3 Bromobenzene (40 mg, 1.27 x 1 (T4 mol) and Pd (PPh3) 4 (17 mg, 1.5 x 10·5 mol) was prepared by the procedure described in Example 4. After refluxing for 5 16 hours under nitrogen, the 'yellow solid precipitate was The main product. The reaction mixture was cooled to room temperature' poured into 100 ml of water and 400 ml of CH2CI2. The organic phase containing yellow sediments was washed 3 times with 100 ml of water and filtered with a G3 glass screening program. The residue (product) was washed three times with 20 ml of CH2C12, dried overnight under high vacuum to give 330 mg of pure product. Yield 10: 99%. Melting point: 202 ° C. Example 7: (β according to the invention) Preparation of matter)

1305537 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (26), 1,3,5-three [3,3",5,5,,-four (5,,-癸基-2 ,2, :5,,2"Trithiophene-5-yl)- 1, oxime: 3', fluorene-terphenyl-5,yl]benzene (xm) Preparation: Compound (XI) (250 mg ' 1.3 Xl〇-4m〇i), i, 3,5-tribromobenzene (i2mg, 3.8x10·5mol) and Pd(PPh3)4 (l〇mg'8.7xl_6mol) were processed by the procedure described in Example 5 Prepared. After refluxing for 24 hours under nitrogen, the compound was isolated using the procedure described in Example 4. 275 mg of the crude product as a brown solid was purified by column chromatography (eluent: toluene) to give 210 mg of a brown solid. Yield: 76%. GPC (polystyrene standard): MP=6900, Dn= 1.02. This paper scale is applicable to China National Standard (CNS) A4 specification (210x297 mm).

Claims (1)

[305537 'i A8 B8 C8 D8 Patent Application No. 92125126 ROC Patent Appln. No.92125126 Amendment to the scope of application for patent replacement page - Annex (II) Amended Claims in rhinese — F,nd YTT, VI. (Submitted on July 11, 2008) (Submitted on July 11, 2008) 1. A compound characterized by having a core composed of multifunctional units and a linear non-co-chain chain at the end. a chemical (Z) core-shell structure of a shell composed of a plurality of oligomeric chains, and the shell is a substituted or unsubstituted 2,5-thiophene or a substituted or unsubstituted 1,4-phenylene unit As a linear conjugated oligomeric chain κ-R)n (Z) wherein K is an η-functional nucleus, wherein the nucleus contains 1,3,5-phenylene unit 10 as a dendritic structure, or the core contains a highly branched polymer As a highly branched structure, L is a linear co-armed oligomeric chain, R is a linear or branched C2-C2Q-alkyl group, monounsaturated or polyunsaturated C2-C2 〇-alkenyl, C2-C2〇- Alkoxy, C2-C2 〇-aralkyl, 15 C2-C2G-oligomer, or C2-C2G-polycarboxyl η is greater than or equal An integer of 3. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, Employees' Consumption Co., Ltd. 2. A compound according to claim 1 of the patent application, characterized in that the shell contains unsubstituted 2,5-thiophene or 2,5-(3,4-extended ethyl The unit of dioxythiophene is used as a linear co-armed oligomeric chain. A compound according to claim 1 or 2, characterized in that the linear co-armed oligomeric chain is a chain having a chain length of 2 to 7 units. 4. A compound according to claim 1 or 2, characterized in that the linear conjugated oligomeric chains are each identical or different at the end-point link, and the 29-92423B-to-one paper size is applicable to the Chinese national standard. (CNS) A4 size (210 X 297 mm) 1305537 C8 -------D8______ VI. Application for patented range or unbranched alkyl or alkoxy end capping. 5. A compound according to item 4 of the patent application, characterized in that the alkyl group or the alkoxy group is unbranched (^/in an alkyl group or a C2-C2 (r alkoxy group. 5 6 · according to the scope of the patent application 4 A compound of the formula wherein the alkyl or alkoxy group is n-hexyl, n-decyl and n-dodecyl. 7. The compound according to claim 1 or 2, which is characterized in that it is at 50 ° C - 30 (Intermediate phase is formed in the TC temperature range. 8. The compound according to claim 1 or 2, characterized in that it is semi-conductive. 9. The compound according to claim 1 or 2, characterized in that The method of preparing a compound according to any one of claims 1 to 9 characterized by having a mobility of at least 1 (T4 cm 2 /Vs), characterized in that a low 15-polymer is prepared by an organometallic reaction. Or a polymer, the reaction comprising: introducing a suitable function selected from the group consisting of an i-organ, an organotin-based or an organoboron group into a dendritic or highly branched core, a linear conjugated oligomeric chain, and a flexible non-co-stranded chain; Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, printing Subsequently, these are connected to each other. 20 The method according to claim 10, characterized in that an oligomer or a polymer is prepared by a Kumada coupling reaction in which two bromine groups are coupled via a Grignard compound using a saturated catalyst. 12. The method according to the first aspect of the patent application, characterized in that an oligomer or a polymer is prepared by a Suzuki coupling reaction, wherein the boron-containing -30 - the paper scale is applicable to the Chinese National Standard (CNS) A4 specification ( 21〇x 297 公发) A8 1305537 ^ _D8_ 6. The patent-scoped group is coupled with a bromine group using a palladium catalyst under alkaline conditions. 13. A compound according to at least one of claims 1 to 9 Application in the electronic component as a semiconductor. 14. The use of a compound according to claim 13 of the patent application is characterized by a field effect transistor, a light-emitting element such as an organic light-emitting diode or a photovoltaic cell, a laser And as a semiconductor in the sensor and the device 15. The application according to the compound of claim 13 or 14 is characterized in that the application form is Film applied in solution 16. Compound according to item 1 of the patent application, which is used as a semiconductor in electronic component 10. Printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs, the Chinese National Standard (CNS) A4 size (210x297 mm)